scholarly journals Coastal hypoxia/anoxia as a source of CH<sub>4</sub> and N<sub>2</sub>O

2009 ◽  
Vol 6 (5) ◽  
pp. 9455-9523 ◽  
Author(s):  
S. W. A. Naqvi ◽  
H. W. Bange ◽  
L. Farías ◽  
P. M. S. Monteiro ◽  
M. I. Scranton ◽  
...  

Abstract. We review here available information on distributions of methane (CH4) and nitrous oxide (N2O) from major, mostly coastal, oxygen (O2)-deficient zones produced due to both natural processes and human activities (mainly eutrophication). Concentrations of both gases in subsurface waters are affected by ambient O2 levels. In the case of CH4, bottom-water O2 content probably affects emission from sediments, believed to be the main source of water-column CH4, as well as its oxidative loss in water itself. Highest CH4 accumulation (several μM) occurs in silled basins having anoxic deep waters such as the Black Sea and the Cariaco Basin. One to two orders of magnitude smaller, but still significant, accumulation also occurs in bottom waters of open margins experiencing anoxia and in silled basins containing suboxic/severely hypoxic waters. In highly eutrophic waters over open continental shelves (such as the upwelling zone off Namibia and the "dead zone" in the Gulf of Mexico) high CH4 concentrations (several hundred nM) may occur in non-sulphidic waters as well, but in these regions it is difficult to differentiate the hypoxia-induced enhancement from in situ production of CH4 in the water column and, sometimes, large inputs of CH4 associated with freshwater runoff or seepage from sediments. Despite the observed CH4 build-up in low-O2 bottom waters, methanotrophic activity severely restricts its emission from the ocean. As a result, an intensification or expansion of coastal hypoxic zones will probably not drastically change the present status where emission from the ocean as a whole forms an insignificant term in the atmospheric CH4 budget. The situation is different for N2O, the production of which is greatly enhanced in severely hypoxic waters, and although it is lost through denitrification in most suboxic and anoxic environments, the peripheries of such environments offer most suitable conditions for its production, with the exception of semi-enclosed/land-locked anoxic basins such as the Black Sea. Most O2-deficient systems serve as strong net sources of N2O to the atmosphere. This is especially true for regions of coastal upwelling with shallow oxygen minimum zones where a dramatic increase in N2O production often occurs in rapidly denitrifying waters. Nitrous oxide emissions from these zones are globally significant, and so their ongoing intensification and expansion is likely to lead to a significant increase in N2O emission from the ocean. However, a meaningful quantitative prediction of this increase is not possible at present because of continuing uncertainties concerning the formative pathways to N2O as well as insufficient data from some key coastal regions.

2010 ◽  
Vol 7 (7) ◽  
pp. 2159-2190 ◽  
Author(s):  
S. W. A. Naqvi ◽  
H. W. Bange ◽  
L. Farías ◽  
P. M. S. Monteiro ◽  
M. I. Scranton ◽  
...  

Abstract. We review here the available information on methane (CH4) and nitrous oxide (N2O) from major marine, mostly coastal, oxygen (O2)-deficient zones formed both naturally and as a result of human activities (mainly eutrophication). Concentrations of both gases in subsurface waters are affected by ambient O2 levels to varying degrees. Organic matter supply to seafloor appears to be the primary factor controlling CH4 production in sediments and its supply to (and concentration in) overlying waters, with bottom-water O2-deficiency exerting only a modulating effect. High (micromolar level) CH4 accumulation occurs in anoxic (sulphidic) waters of silled basins, such as the Black Sea and Cariaco Basin, and over the highly productive Namibian shelf. In other regions experiencing various degrees of O2-deficiency (hypoxia to anoxia), CH4 concentrations vary from a few to hundreds of nanomolar levels. Since coastal O2-deficient zones are generally very productive and are sometimes located close to river mouths and submarine hydrocarbon seeps, it is difficult to differentiate any O2-deficiency-induced enhancement from in situ production of CH4 in the water column and its inputs through freshwater runoff or seepage from sediments. While the role of bottom-water O2-deficiency in CH4 formation appears to be secondary, even when CH4 accumulates in O2-deficient subsurface waters, methanotrophic activity severely restricts its diffusive efflux to the atmosphere. As a result, an intensification or expansion of coastal O2-deficient zones will probably not drastically change the present status where emission from the ocean as a whole forms an insignificant term in the atmospheric CH4 budget. The situation is different for N2O, the production of which is greatly enhanced in low-O2 waters, and although it is lost through denitrification in most suboxic and anoxic environments, the peripheries of such environments offer most suitable conditions for its production, with the exception of enclosed anoxic basins. Most O2-deficient systems serve as strong net sources of N2O to the atmosphere. This is especially true for coastal upwelling regions with shallow O2-deficient zones where a dramatic increase in N2O production often occurs in rapidly denitrifying waters. Nitrous oxide emissions from these zones are globally significant, and so their ongoing intensification and expansion is likely to lead to a significant increase in N2O emission from the ocean. However, a meaningful quantitative prediction of this increase is not possible at present because of continuing uncertainties concerning the formative pathways to N2O as well as insufficient data from key coastal regions.


2016 ◽  
Vol 13 (4) ◽  
pp. 1105-1118 ◽  
Author(s):  
Damian L. Arévalo-Martínez ◽  
Annette Kock ◽  
Carolin R. Löscher ◽  
Ruth A. Schmitz ◽  
Lothar Stramma ◽  
...  

Abstract. Recent observations in the eastern tropical South Pacific (ETSP) have shown the key role of meso- and submesoscale processes (e.g. eddies) in shaping its hydrographic and biogeochemical properties. Off Peru, elevated primary production from coastal upwelling in combination with sluggish ventilation of subsurface waters fuels a prominent oxygen minimum zone (OMZ). Given that nitrous oxide (N2O) production–consumption processes in the water column are sensitive to oxygen (O2) concentrations, the ETSP is a region of particular interest to investigate its source–sink dynamics. To date, no detailed surveys linking mesoscale processes and N2O distributions as well as their relevance to nitrogen (N) cycling are available. In this study, we present the first measurements of N2O across three mesoscale eddies (two mode water or anticyclonic and one cyclonic) which were identified, tracked, and sampled during two surveys carried out in the ETSP in November–December 2012. A two-peak structure was observed for N2O, wherein the two maxima coincide with the upper and lower boundaries of the OMZ, indicating active nitrification and partial denitrification. This was further supported by the abundances of the key gene for nitrification, ammonium monooxygenase (amoA), and the gene marker for N2O production during denitrification, nitrite reductase (nirS). Conversely, we found strong N2O depletion in the core of the OMZ (O2 < 5 µmol L−1) to be consistent with nitrite (NO2−) accumulation and low levels of nitrate (NO3−), thus suggesting active denitrification. N2O depletion within the OMZ's core was substantially higher in the centre of mode water eddies, supporting the view that eddy activity enhances N-loss processes off Peru, in particular near the shelf break where nutrient-rich, productive waters from upwelling are trapped before being transported offshore. Analysis of eddies during their propagation towards the open ocean showed that, in general, “ageing” of mesoscale eddies tends to decrease N2O concentrations through the water column in response to the reduced supply of material to fuel N loss, although hydrographic variability might also significantly impact the pace of the production–consumption pathways for N2O. Our results evidence the relevance of mode water eddies for N2O distribution, thereby improving our understanding of the N-cycling processes, which are of crucial importance in times of climate change and ocean deoxygenation.


2020 ◽  
Author(s):  
Alan Matthews ◽  
Ayelet Benkovitz ◽  
Nadya Teutsch ◽  
Simon Poulton ◽  
Miryam Bar-Matthews ◽  
...  

&lt;p&gt;Sapropels S5 and S7 formed in the semi-enclosed Eastern Mediterranean Sea &amp;#160;during peak interglacial periods MIS5e and MIS7a, respectively. This study investigates the dynamics of &amp;#160;water column redox change during their formation, through Fe isotope and Fe speciation studies of cores taken at 2550 m depth at site ODP-967 south of Cyprus. Both sapropels show an inverse correlation between &amp;#948;&lt;sup&gt;56&lt;/sup&gt;Fe and Fe&lt;sub&gt;T&lt;/sub&gt;/Al, with slopes mostly matching that found for the Black Sea, pointing to a benthic shelf to basin shuttle of Fe and subsequent precipitation of Fe sulphides in highly euxinic bottom waters. An exception to these Black Sea-type trends occurs during the later, peak stages of S7, where the negative &amp;#948;&lt;sup&gt;56&lt;/sup&gt;Fe - Fe&lt;sub&gt;T&lt;/sub&gt;/Al slope shallows. Fe speciation studies reveal that the dominant highly reactive Fe phase (Fe&lt;sub&gt;HR&lt;/sub&gt;) in the sapropels is pyrite, with Fe (oxyhydr)oxides forming the second major mineral component. Fe&lt;sub&gt;HR&lt;/sub&gt;/Fe&lt;sub&gt;T&lt;/sub&gt; plots show increased strengthening of anoxic water conditions during the transformation from pre-sapropel sediment into the sapropel. Nevertheless, despite the evidence for highly euxinic conditions from both Fe isotopes and high Mo concentrations in the sapropels, Fe&lt;sub&gt;py&lt;/sub&gt;/Fe&lt;sub&gt;HR&lt;/sub&gt; ratios remain below values commonly used to identify water column euxinia. This apparent contradiction is ascribed to the sedimentary preservation of a high flux of crystalline Fe (oxyhydr)oxide minerals to the basin, which resulted in a relatively low degree of sulphidation, despite the presence of euxinic bottom waters.&amp;#160; Thus, the operationally defined ferruginous/euxinic boundary for Eastern Mediterranean Sea sapropels is better placed at Fe&lt;sub&gt;py&lt;/sub&gt;/Fe&lt;sub&gt;HR&lt;/sub&gt; = 0.6, which is somewhat below the usually ascribed lower limit of 0.7. Consistent with the significant presence of crystalline Fe (oxyhydr)oxides, the change in the &amp;#948;&lt;sup&gt;56&lt;/sup&gt;Fe - Fe&lt;sub&gt;T&lt;/sub&gt;/Al slope during peak S7 is ascribed to an enhanced monsoon-driven flux of detrital Fe(III) oxides from the River Nile into the Eastern Mediterranean basin. The euxinic water column conditions that developed in sapropels S5 and S7 are interpreted to reflect the positive balance between dissolved sulphide formation and rates of reductive dissolution of Fe (oxyhydr)oxide minerals. Both of these parameters in turn depend on the extent to which water overturn times are reduced during sapropel formation. Water overturn rate is therefore considered to define the strength of euxinic water column conditions during these periods of organic carbon-rich sedimentation.&lt;/p&gt;


2015 ◽  
Vol 12 (12) ◽  
pp. 9243-9273 ◽  
Author(s):  
D. L. Arévalo-Martínez ◽  
A. Kock ◽  
C. R. Löscher ◽  
R. A. Schmitz ◽  
L. Stramma ◽  
...  

Abstract. Recent observations in the eastern tropical South Pacific (ETSP) demonstrated the key role of meso- and submesoscale processes (e.g. eddies) in shaping its hydrographic and biogeochemical properties. Off Peru, elevated primary production from coastal upwelling in combination with sluggish ventilation of subsurface waters fuels a prominent oxygen minimum zone (OMZ). Given that nitrous oxide (N2O) production/consumption processes on the water column are sensitive to oxygen (O2) concentrations, the ETSP is a region of particular interest to investigate its source-sink dynamics. To date, no detailed surveys linking mesoscale processes and N2O distributions as well as their relevance to nitrogen (N) cycling are available. In this study, we present the first measurements of N2O across three mesoscale eddies (two mode water or anticyclonic and one cyclonic) which were identified, tracked and sampled during two surveys carried out in the ETSP in November-December 2012. A "two peak" structure was observed for N2O, wherein the two maxima coincide with the upper and lower boundaries of the OMZ, indicating active nitrification and partial denitrification. This was further supported by the abundances of the key gene for nitrification amoA and the gene marker for N2O production during denitrification, nirS. Conversely, we found strong N2O depletion in the core of the OMZ (O2 < 5 μmol L−1) to be consistent with nitrite (NO2−) accumulation and low levels of nitrate (NO3−), thus suggesting active denitrification. N2O depletion within the OMZ's core was substantially higher in the center of mode water eddies, supporting the view that eddy activity enhances N-loss processes off Peru, in particular near the shelf break where nutrient-rich, productive waters from upwelling are trapped before being transported offshore. Analysis of eddies during their propagation towards the open ocean showed that, in general, "aging" of mesoscale eddies tends to decrease N2O concentrations through the water column in response to reduced supply of material to fuel N-loss, although hydrographic variability might also significantly impact the pace of the production/consumption pathways for N2O. Our results demonstrate the relevance of mode water eddies for N2O distribution, thereby improving our understanding of the N-cycling processes, which are of crucial importance in times of climate change and ocean deoxygenation.


2021 ◽  
Vol 10 (3) ◽  
Author(s):  
Mariia Pavlovska ◽  
Ievgeniia Prekrasna ◽  
Evgen Dykyi ◽  
Andrii Zotov ◽  
Artem Dzhulai ◽  
...  

2013 ◽  
Vol 10 (6) ◽  
pp. 3943-3962 ◽  
Author(s):  
A. Capet ◽  
J.-M. Beckers ◽  
M. Grégoire

Abstract. The Black Sea northwestern shelf (NWS) is a shallow eutrophic area in which the seasonal stratification of the water column isolates the bottom waters from the atmosphere. This prevents ventilation from counterbalancing the large consumption of oxygen due to respiration in the bottom waters and in the sediments, and sets the stage for the development of seasonal hypoxia. A three-dimensional (3-D) coupled physical–biogeochemical model is used to investigate the dynamics of bottom hypoxia in the Black Sea NWS, first at seasonal and then at interannual scales (1981–2009), and to differentiate its driving factors (climatic versus eutrophication). Model skills are evaluated by a quantitative comparison of the model results to 14 123 in situ oxygen measurements available in the NOAA World Ocean and the Black Sea Commission databases, using different error metrics. This validation exercise shows that the model is able to represent the seasonal and interannual variability of the oxygen concentration and of the occurrence of hypoxia, as well as the spatial distribution of oxygen-depleted waters. During the period 1981–2009, each year exhibits seasonal bottom hypoxia at the end of summer. This phenomenon essentially covers the northern part of the NWS – which receives large inputs of nutrients from the Danube, Dniester and Dnieper rivers – and extends, during the years of severe hypoxia, towards the Romanian bay of Constanta. An index H which merges the aspects of the spatial and temporal extension of the hypoxic event is proposed to quantify, for each year, the intensity of hypoxia as an environmental stressor. In order to explain the interannual variability of H and to disentangle its drivers, we analyze the long time series of model results by means of a stepwise multiple linear regression. This statistical model gives a general relationship that links the intensity of hypoxia to eutrophication and climate-related variables. A total of 82% of the interannual variability of H is explained by the combination of four predictors: the annual riverine nitrate load (N), the sea surface temperature in the month preceding stratification (Ts), the amount of semi-labile organic matter accumulated in the sediments (C) and the sea surface temperature during late summer (Tf). Partial regression indicates that the climatic impact on hypoxia is almost as important as that of eutrophication. Accumulation of organic matter in the sediments introduces an important inertia in the recovery process after eutrophication, with a typical timescale of 9.3 yr. Seasonal fluctuations and the heterogeneous spatial distribution complicate the monitoring of bottom hypoxia, leading to contradictory conclusions when the interpretation is done from different sets of data. In particular, it appears that the recovery reported in the literature after 1995 was overestimated due to the use of observations concentrated in areas and months not typically affected by hypoxia. This stresses the urgent need for a dedicated monitoring effort in the Black Sea NWS focused on the areas and months concerned by recurrent hypoxic events.


2018 ◽  
Vol 15 (20) ◽  
pp. 6127-6138 ◽  
Author(s):  
Qixing Ji ◽  
Claudia Frey ◽  
Xin Sun ◽  
Melanie Jackson ◽  
Yea-Shine Lee ◽  
...  

Abstract. Nitrous oxide (N2O) is a greenhouse gas and an ozone depletion agent. Estuaries that are subject to seasonal anoxia are generally regarded as N2O sources. However, insufficient understanding of the environmental controls on N2O production results in large uncertainty about the estuarine contribution to the global N2O budget. Incubation experiments with nitrogen stable isotope tracer were used to investigate the geochemical factors controlling N2O production from denitrification in the Chesapeake Bay, the largest estuary in North America. The highest potential rates of water column N2O production via denitrification (7.5±1.2 nmol-N L−1 h−1) were detected during summer anoxia, during which oxidized nitrogen species (nitrate and nitrite) were absent from the water column. At the top of the anoxic layer, N2O production from denitrification was stimulated by addition of nitrate and nitrite. The relative contribution of nitrate and nitrite to N2O production was positively correlated with the ratio of nitrate to nitrite concentrations. Increased oxygen availability, up to 7 µmol L−1 oxygen, inhibited both N2O production and the reduction of nitrate to nitrite. In spring, high oxygen and low abundance of denitrifying microbes resulted in undetectable N2O production from denitrification. Thus, decreasing the nitrogen input into the Chesapeake Bay has two potential impacts on the N2O production: a lower availability of nitrogen substrates may mitigate short-term N2O emissions during summer anoxia; and, in the long-run (timescale of years), eutrophication will be alleviated and subsequent reoxygenation of the bay will further inhibit N2O production.


2012 ◽  
Vol 9 (8) ◽  
pp. 2989-3002 ◽  
Author(s):  
K. Schelde ◽  
P. Cellier ◽  
T. Bertolini ◽  
T. Dalgaard ◽  
T. Weidinger ◽  
...  

Abstract. Nitrous oxide (N2O) emissions from agricultural land are variable at the landscape scale due to variability in land use, management, soil type, and topography. A field experiment was carried out in a typical mixed farming landscape in Denmark, to investigate the main drivers of variations in N2O emissions, measured using static chambers. Measurements were made over a period of 20 months, and sampling was intensified during two weeks in spring 2009 when chambers were installed at ten locations or fields to cover different crops and topography and slurry was applied to three of the fields. N2O emissions during spring 2009 were relatively low, with maximum values below 20 ng N m−2 s−1. This applied to all land use types including winter grain crops, grasslands, meadows, and wetlands. Slurry application to wheat fields resulted in short-lived two-fold increases in emissions. The moderate N2O fluxes and their moderate response to slurry application were attributed to dry soil conditions due to the absence of rain during the four previous weeks. Cumulative annual emissions from two arable fields that were both fertilized with mineral fertilizer and manure were large (17 kg N2O-N ha−1 yr−1 and 5.5 kg N2O-N ha−1 yr−1) during the previous year when soil water conditions were favourable for N2O production during the first month following fertilizer application. Our findings confirm the importance of weather conditions as well as nitrogen management on N2O fluxes.


2017 ◽  
Vol 14 (20) ◽  
pp. 4795-4813 ◽  
Author(s):  
Alexander Galán ◽  
Bo Thamdrup ◽  
Gonzalo S. Saldías ◽  
Laura Farías

Abstract. The upwelling system off central Chile (36.5° S) is seasonally subjected to oxygen (O2)-deficient waters, with a strong vertical gradient in O2 (from oxic to anoxic conditions) that spans a few metres (30–50 m interval) over the shelf. This condition inhibits and/or stimulates processes involved in nitrogen (N) removal (e.g. anammox, denitrification, and nitrification). During austral spring (September 2013) and summer (January 2014), the main pathways involved in N loss and its speciation, in the form of N2 and/or N2O, were studied using 15N-tracer incubations, inhibitor assays, and the natural abundance of nitrate isotopes along with hydrographic information. Incubations were developed using water retrieved from the oxycline (25 m depth) and bottom waters (85 m depth) over the continental shelf off Concepción, Chile. Results of 15N-labelled incubations revealed higher N removal activity during the austral summer, with denitrification as the dominant N2-producing pathway, which occurred together with anammox at all times. Interestingly, in both spring and summer maximum potential N removal rates were observed in the oxycline, where a greater availability of oxygen was observed (maximum O2 fluctuation between 270 and 40 µmol L−1) relative to the hypoxic bottom waters ( <  20 µmol O2 L−1). Different pathways were responsible for N2O produced in the oxycline and bottom waters, with ammonium oxidation and dissimilatory nitrite reduction, respectively, as the main source processes. Ammonium produced by dissimilatory nitrite reduction to ammonium (DNiRA) could sustain both anammox and nitrification rates, including the ammonium utilized for N2O production. The temporal and vertical variability of δ15N-NO3− confirms that multiple N-cycling processes are modulating the isotopic nitrate composition over the shelf off central Chile during spring and summer. N removal processes in this coastal system appear to be related to the availability and distribution of oxygen and particles, which are a source of organic matter and the fuel for the production of other electron donors (i.e. ammonium) and acceptors (i.e. nitrate and nitrite) after its remineralization. These results highlight the links between several pathways involved in N loss. They also establish that different mechanisms supported by alternative N substrates are responsible for substantial accumulation of N2O, which are frequently observed as hotspots in the oxycline and bottom waters. Considering the extreme variation in oxygen observed in several coastal upwelling systems, these findings could help to understand the ecological and biogeochemical implications due to global warming where intensification and/or expansion of the oceanic OMZs is projected.


2020 ◽  
Vol 117 (22) ◽  
pp. 11954-11960 ◽  
Author(s):  
Simon Yang ◽  
Bonnie X. Chang ◽  
Mark J. Warner ◽  
Thomas S. Weber ◽  
Annie M. Bourbonnais ◽  
...  

Assessment of the global budget of the greenhouse gas nitrous oxide (N2O) is limited by poor knowledge of the oceanicN2O flux to the atmosphere, of which the magnitude, spatial distribution, and temporal variability remain highly uncertain. Here, we reconstruct climatologicalN2O emissions from the ocean by training a supervised learning algorithm with over 158,000N2O measurements from the surface ocean—the largest synthesis to date. The reconstruction captures observed latitudinal gradients and coastal hot spots ofN2O flux and reveals a vigorous global seasonal cycle. We estimate an annual meanN2O flux of 4.2 ± 1.0 Tg N⋅y−1, 64% of which occurs in the tropics, and 20% in coastal upwelling systems that occupy less than 3% of the ocean area. ThisN2O flux ranges from a low of 3.3 ± 1.3 Tg N⋅y−1in the boreal spring to a high of 5.5 ± 2.0 Tg N⋅y−1in the boreal summer. Much of the seasonal variations in globalN2O emissions can be traced to seasonal upwelling in the tropical ocean and winter mixing in the Southern Ocean. The dominant contribution to seasonality by productive, low-oxygen tropical upwelling systems (>75%) suggests a sensitivity of the globalN2O flux to El Niño–Southern Oscillation and anthropogenic stratification of the low latitude ocean. This ocean flux estimate is consistent with the range adopted by the Intergovernmental Panel on Climate Change, but reduces its uncertainty by more than fivefold, enabling more precise determination of other terms in the atmosphericN2O budget.


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